CN102479950A - Titanium niobate composite material, preparation method thereof, and cathode and battery containing the same - Google Patents

Titanium niobate composite material, preparation method thereof, and cathode and battery containing the same Download PDF

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CN102479950A
CN102479950A CN2010105605799A CN201010560579A CN102479950A CN 102479950 A CN102479950 A CN 102479950A CN 2010105605799 A CN2010105605799 A CN 2010105605799A CN 201010560579 A CN201010560579 A CN 201010560579A CN 102479950 A CN102479950 A CN 102479950A
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composite material
preparation
boron
nitrogen
carbon
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CN102479950B (en
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卢侠
简泽浪
方铮
胡勇胜
李泓
王兆翔
黄学杰
陈立泉
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Institute of Physics of CAS
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Abstract

The invention relates to a titanium niobate composite material, a preparation method thereof, and a cathode and a battery containing the composite material. The titanium niobate composite material is represented as BxCyNz-LaTibMcNbdOe, wherein BxCyNz represents a compound containing boron carbon or carbon nitrogen or boron carbon nitrogen; L represents Li or Na, preferably Li; M is one element selected from Al, B, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta, N and P; x, y, z, a, b, c, d and e represent mole percentages, x is no less than 0 and less than 1, y is larger than 0 and less than 1, z is no less than 0 and less than 1, a is no less than 0 and no larger than 0.2, b is larger than 0.8 and no larger than 1.1, c is no less than 0 and less than 0.2, d is larger than 1.95 and no larger than 2.1, e is no less than 6.8 and no larger than 7, and x and y are not 0 at the same time. The composite material disclosed herein and used as a cathode material of a lithium ion battery has the advantages of high coulombic efficiency, high ionic and electric conductance, good cycling performance of high-rate charge and discharge, high safety, no pollution, and low price.

Description

Titanium niobate composite material, its preparation method and contain the negative pole and the battery of this composite material
Technical field
The present invention relates to metal oxide composite, its preparation method and contain the negative pole and the battery of this composite material; In particular to a kind of negative pole and battery that contains titanium niobate composite material, its preparation method of boron carbon or carbon nitrogen or boron carboritride and contain this composite material.
Background technology
(Mater.Chem.Phys., 13 (1985) 85-90 in early days; J.Solid State Chem.4,136-142 (1981)) to TiNb 2O 7Research concentrate on the preparation of its material, self optical property, reduzate and as the electrode material of photovoltaic cell.People such as L.G.J.De Harrt are with highly purified TiO 2Powder and Nb 2O 5After the powder, under 1200 ℃, fire, obtain TiNb 2O 7This is the semiconductor material with wide forbidden band that a kind of energy gap is approximately 3.0eV, and the absorbing wavelength of ultraviolet-visible is slightly larger than 400nm, and the current potential with respect to standard calomel electrode in the NaOH of 1mol/L solution is-0.9V to can be used as the light anode material and use.
In the meeting of the international lithium electricity of the Montreal, CAN on June 27th, 2010, professor Goodenough is to TiNb 2O 7Report, but do not provide any ins and outs about this material.According to Goodenough professor's result, the TiNb that carbon coats 2O 7In the discharge range of 2.5～1.0V, capacity also has good performance in the first five all charge and discharge cycles in the circulation in first three ten week about 270mAh/g.This with market on business-like lithium cell cathode material lithium titanate (Li 4Ti 5O 12) compare bigger energy storage advantage is arranged, the theoretical capacity of lithium titanate is greatly about 175mAh/g, though lithium titanate has better cycle performance, itself electronic conductance is not high, needs relevant modification to handle could to improve its electricity to lead.
As a kind of wide-band gap material, TiNb 2O 7Electronic conductance and bad.After professor Goodenough carried out carbon coating processing to it, the electronic conductance of material improved.But in practical application, require TiNb 2O 7Electrode material has higher electronic conductance and ionic conductance, stable structure, good electrical conductivity, stable crystal boundary and smaller volume deformation simultaneously; And unobstructed ion transport; And adopt above-mentioned improving one's methods to be difficult to obtain expected effect, need further to improve.
Summary of the invention
The objective of the invention is in order to improve the TiNb that existing carbon coats 2O 7The continuous present situation of loss of the big even not reversible and capacity of structural change in not high, the cyclic process of conductivity provides a kind of high conduction niobates composite material that contains boron carbon or carbon nitrogen or boron carbon nitrogen during as the serondary lithium battery negative material.This composite material is to form through the high conductive compound that introducing contains boron carbon or carbon nitrogen or boron carbon nitrogen.The present invention also provides the preparation method of above-mentioned composite material and adopts the negative pole and the battery of above-mentioned Composite Preparation.
The technical scheme that realizes the object of the invention is following:
A kind of titanium niobate composite material, this composite material has following general formula:
B xC yN z-L aTi bM cNb dO e
Wherein, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound;
L can be preferably Li for Li or Na;
M is selected from a kind of among Al, B, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta, N and the P;
X, y, z, a, b, c, d and e represent molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0≤a≤0.2,0.8＜b≤1.1,0≤c＜0.2,1.95＜d≤2.1,6.8≤e≤7, and x and z are not zero simultaneously.
Preferably, 0≤x＜1,0＜y＜1,0＜z＜1.
More preferably, x=0,0＜y＜1,0＜z＜1, promptly this composite material is the titanium niobate composite material that contains the aerobic room of carbon nitrogen coating, the first all charge/discharge capacities of the titanium niobate composite material that this carbon nitrogen coats all are higher than other clad materials.
In the above-mentioned titanium niobate composite material, said boron carbon or carbon nitrogen or the boron carbon nitrogen compound B of containing xC yN zBe coated on L aTi bM cNb dO eThe surface of material forms B xC yN zAnd L aTi bM cNb dO eThe interface, said L aTi bM cNb dO eBe granular materials, L aTi bM cNb dO eAnd L aTi bM cNb dO eGranule depend on B xC yN zConnect.
In the above-mentioned titanium niobate composite material, said boron carbon or carbon nitrogen or the boron carbon nitrogen compound B of containing xC yN zThe quality percentage composition be 0.1%-20%, be preferably 1%-10%.
In the above-mentioned titanium niobate composite material, when x=0, said B xC yN zThe quality percentage composition of middle nitrogen is 0.01%-30%, is preferably 0.1%-15%, and the quality percentage composition of nitrogen in said composite material is 0.001%-6%, is preferably 0.1%-1.5%; When x ≠ 0, said B xC yN zThe quality percentage composition of middle nitrogen is 0%-20%, is preferably 0.1%-10%, and the quality percentage composition of nitrogen in said composite material is 0%-4%, is preferably 0.1%-1%.
In the above-mentioned titanium niobate composite material, when z=0, said B xC yN zThe quality percentage composition of middle boron is 0.01%-15%, is preferably 0.1%-8%, and the quality percentage composition of boron in said composite material is 0.001%-3%, is preferably 0.1%-1.5%; When z ≠ 0, said B xC yN zThe quality percentage composition of middle boron is 0%-10%, is preferably 0.1%-5%, and the quality percentage composition of boron in said composite material is 0%-2%, is preferably 0.1%-1%.
The present invention also provides the preparation method of above-mentioned composite material, and this preparation method can comprise the steps:
With L aTi bM cNb dO eEvenly mix with the material that contains boron carbon or carbon nitrogen or boron carboritride, in inert atmosphere such as nitrogen or argon gas, said mixture is warming up to 400～700 ℃ from room temperature with 5 ℃/minute speed; And under this temperature, kept 4 hours; Fully after the reaction, cooling obtains said composite material;
Wherein, L is Li or Na, is preferably Li;
M is selected from a kind of among Al, B, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta, N and the P;
X, y, z, a, b, c, d and e represent molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0≤a≤0.2,0.8＜b≤1.1,0≤c＜0.2,1.95＜d≤2.1,6.8≤e≤7, and x and z are not zero simultaneously.
Preferably, among the preparation method of above-mentioned composite material, the said material that contains boron carbon or carbon nitrogen or boron carboritride is ionic liquid 1-ethyl-3-methylimidazole dicyanamide salt ([EMIm] [N (CN) 2]), the two fluoroform sulfimide salt ([BCNIm] [Tf2N]), 1 of ionic liquid 1-butyl-3-methylimidazole; 4; 5-trimethyl-3-perfluoro capryl-1; 2,4-triazole tetrafluoroborate, 1-cyanogen methyl-3-methyl imidazolium tetrafluoroborate, 1, two (cyanogen) tetrafluoroborates of 3-, triphenyl borine, Glucosamine or phthalocyanine.
Among the preparation method of above-mentioned composite material, said L aTi bM cNb dO eThe preparation method can comprise the steps (solid sintering technology):
According to L aTi bM cNb dO eIn the proportioning of each element, with TiO 2Powder, Nb 2O 5After powder, L source and the M source batching, add solvent, for example absolute ethyl alcohol, water or acetone diluted become white paste; With said pastel ball milling after 10-24 hour; Dry under 50-70 ℃, the cooling back is warming up between 1200～1400 ℃ with 5 ℃/minute speed, and after being incubated 24 hours; Cooling promptly gets.
Preferably, said L source is the lithium source, for example is lithium carbonate, lithium acetate, lithium hydroxide or lithium oxalate;
Preferably, said M source is the oxide that contains Al, B, La or Ta, or contains the material of Al, B, La or Ta oxide after the decomposes;
Preferably, said L aTi bM cNb dO eThe preparation method also comprise the product that obtains carried out 24 hours high energy millings, obtain 100-500nm, be preferably the step of 200nm granular materials;
Preferably, said L aTi bM cNb dO eThe preparation method also comprise with the product that obtains under temperature 700-900 ℃ reducing atmosphere, for example hydrogen; Perhaps inert atmosphere, for example step of heat treatment in nitrogen or the argon gas.This step is for realizing the step in oxygen room, and in above-mentioned titanium niobate composite material, the situation that the aerobic room exists can be represented in 6.8≤e≤7; Concrete operations can for: with the low price cation, alternative Ti such as Al, Fe, B for example are perhaps with the high price anion; N for example, replacement O such as P realize; Perhaps in reduction or inert atmosphere, heat-treat; Perhaps use above-mentioned any two kinds of methods or three kinds of methods to realize the oxygen room simultaneously.
In a specific embodiments of the present invention, the preparation method of titanium niobate composite material of the present invention is a solid sintering technology, and this method comprises the steps:
A. with TiO 2Powder and Nb 2O 5Powder adds solvent (for example absolute ethyl alcohol, water or acetone) and is diluted to white paste after being n (Ti)/n (Nb)=0.5 batching according to mol ratio; Above-mentioned pastel is through dry under a little more than the environment of room temperature (promptly 50～70 ℃) behind the ball milling, and being pressed into diameter after the cooling is 30mm, and thickness is the tablet of 5mm; With above-mentioned white plates as for Al 2O 3In the crucible, Fast Heating (with the heating rate of 5 ℃/min) in air then, temperature and obtain pure sample after being incubated 24 hours between 1200～1400 ℃.Sample with obtaining the um level after the pure sample grinding of firing can obtain the particle about 200nm through after 24 hours the high-energy ball millings;
B. the material and ionic liquid [the EMIm] [N (CN) that step a are obtained 2] evenly mix after, in inert atmosphere conductivity cell formula stove, the mixture that obtains is risen to 400～700 ℃ from room temperature, and under this temperature, kept 4 hours with 5 ℃/minute speed, ionic liquid is fully reacted, obtain said composite material after the cooling.
If the preparatory titanium niobate material of embedding lithium, then heating-up temperature needs suitably to reduce in the preparation process, and reducing the volatilization of lithium, actual temp changes based on the variation in lithium source.
For the titanium niobate material of preparatory embedding lithium, the lithium source can be lithium carbonate, lithium acetate, lithium hydroxide or lithium oxalate.
Among the preparation method of above-mentioned composite material, said L aTi bM cNb dO eThe preparation method can comprise the steps (sol-gel process):
(1) titanium tetraisopropylate and ammoniacal liquor reaction are formed white precipitate, add nitric acid then white precipitate is dissolved fully, form transparent TiO (NO 3) 2Solution;
(2) with Nb (OH) 5With citric acid be that 1: 5 ratio is dissolved in the deionized water with mol ratio, then, add the TiO (NO of preparation in the step (1) 3) 2Solution, the mixed liquor that obtains are incubated down at 40～60 ℃ and form colloidal sol, continue heating and also remain between 80～100 ℃, form gel;
(3) heating rate of the gel that makes with 5 ℃/minute is warming up between 1000～1300 ℃, and is incubated 24 hours, cooling promptly gets;
Preferably, said L aTi bM cNb dO eThe preparation method also comprise the product that obtains carried out 24 hours high energy millings, obtain 100-500nm, be preferably the step of the granular materials of 200nm;
Preferably, said L aTi bM cNb dO eThe preparation method also comprise with the product that obtains under temperature 700-900 ℃ reducing atmosphere, for example hydrogen; Perhaps inert atmosphere, for example step of heat treatment in nitrogen or the argon gas.This step is for realizing the step in oxygen room, and in above-mentioned titanium niobate composite material, the situation that the aerobic room exists can be represented in 6.8≤e≤7; Concrete operations can for: with the low price cation, alternative Ti such as Al, Fe, B for example are perhaps with the high price anion; N for example, replacement O such as P realize; Perhaps in reduction or inert atmosphere, heat-treat; Perhaps use above-mentioned any two kinds of methods or three kinds of methods to realize the oxygen room simultaneously.
In a specific embodiments of the present invention, the preparation method of titanium niobate composite material of the present invention is a sol-gel process, and this method comprises the steps:
A. prepare predecessor TiO (NO 3) 2: a certain amount of high-purity titanium tetraisopropylate and ammoniacal liquor reaction are formed white precipitate, add nitric acid then and make white precipitate dissolve the transparent TiO (NO of formation fully 3) 2Solution for standby;
B. with high-purity Nb (OH) 5With citric acid in molar ratio (1: 5) be dissolved in the deionized water, be the TiO (NO that n (Ti)/n (Nb)=0.5 adds step a preparation then in molar ratio 3) 2Solution forms colloidal sol with mixed solution 40～60 ℃ of insulations, continues heating then and remain between 80～100 ℃ to form gel;
C. the gel heating rate with 5 ℃/min in air atmosphere that step b is prepared is warming up between 1000～1300 ℃, and is incubated 24 hours, is cooled to the TiNb that room temperature can obtain pure sample subsequently 2O 7
D. with the TiNb of pure sample 2O 7In hydrogen, 700-900 ℃ was heated several hours down, can obtain the titanium niobate material TiNb in aerobic room 2O 6.9
E. with the titanium niobate material TiNb in aerobic room 2O 6.9With ionic liquid [EMIm] [N (CN) 2] evenly mix after, in inert atmosphere conductivity cell formula stove, the mixture that obtains is risen to 400～700 ℃ from room temperature, and under this temperature, kept 4 hours with 5 ℃/minute speed, ionic liquid is fully reacted, obtain said composite material after the cooling.
The present invention also provides the electrode material of above-mentioned titanium niobate composite material at serondary lithium battery, the for example purposes in the negative material.Particularly, the present invention provides a kind of negative pole, and this negative pole comprises collector and load on the negative material on this collector that said negative material contains above-mentioned composite material.Wherein, collector can adopt the known common negative current collector of this field of batteries, and there is no particular limitation.The present invention also provides a kind of lithium battery, and this battery comprises positive pole, negative pole and electrolyte, and said negative pole is the above-mentioned negative pole that contains composite material of the present invention.Adopt the titanium niobate composite material that contains boron carbon or carbon nitrogen or boron carboritride of the present invention to be applicable to various energy storage devices as the above-mentioned serondary lithium battery of negative pole; For example can be applied to portable energy-storing equipment, electric automobile and electric tool, back-up source, redundant electrical power, be not limited to this.
Compared with prior art, the present invention possesses following beneficial effect at least:
1, the present invention contains the negative pole of the titanium niobate composite material of boron carbon or carbon nitrogen or boron carboritride as secondary lithium battery; Its first all discharge capacity (0.1C) is basically more than 290mAh/g; And good cycle performance is arranged; Be much better than market on lithium titanate material, first all discharge capacities (0.1C) are basically at 160mAh/g, are one of potential materials that replaces lithium titanate;
2, the present invention introduces the high conductive compound that contains boron carbon or carbon nitrogen or boron carbon nitrogen in metal oxide-type materials such as titanium niobate, and its effect can simply be described as: can reduce in the charge and discharge process lithium ion greatly at B xC yN zWith L aTi bM cNb dO eMigration activation energy at the interface, the reduction of this migration barrier helps to quicken the diffusion of lithium ion, improve lithium ion active material with contain boron carbon or carbon nitrogen or boron carboritride between mobile, can improve the high rate performance of this composite material preferably;
3, with the material compared that only coats with carbon; The conductivity of composite material of the high conductive compound that contains boron carbon or carbon nitrogen or boron carbon nitrogen of the present invention is better; Because in preparation process, possibly form the surface that the fabulous titanium nitride material of electric conductivity is distributed in active material; This will improve the electronic conductance of material greatly, improve discharging and recharging and high rate performance of compound;
4, at L aTi bM cNb dO eParticle surface coats one deck B xC yN zMaterial, because chemical bond, the interaction of Coulomb force etc. can increase surperficial stability, increases the ability of anti-deformation of active material, the stability when improving useful life on the interface also is significantly improved;
5, method for coating is simple, and ionic liquid is coated in the surface at particle, can guarantee the uniformity of coating layer, from single carbon source to B xC yN zThe source is not only a change of elements, and the huge variation on interface performance has great application prospect especially;
6, contain the negative material that titanium niobate composite material of the present invention can be used as lithium ion battery, higher coulombic efficiency and ion, electronic conductance are arranged, discharged and recharged better cycle performance under the big multiplying power; Safe; Pollution-free, low price, technology is simple; Be widely used, be expected to replace now the lithium titanate (Li of broad research 4Ti 5O 12) material, can be applied to portable energy-storing equipment, electric automobile and electric tool, back-up source, redundant electrical power etc.
Description of drawings
Below, specify embodiments of the invention in conjunction with accompanying drawing, wherein:
Fig. 1 is pure phase TiNb 2O 7X ray diffracting spectrum;
Fig. 2 is pure phase TiNb 2O 7And the UV, visible light optical absorption spectra of corresponding composite material;
Fig. 3 (a) is pure phase TiNb under the ar gas environment 2O 7The thermogravimetric differential thermal curve; (b) be the thermogravimetric differential thermal curve of composite material under corresponding argon gas and the oxygen atmosphere;
Fig. 4 is the charging and discharging curve of titanium niobate composite material of the present invention; And
Fig. 5 is the charge and discharge cycles process of titanium niobate composite material of the present invention.
Concrete execution mode
Below in conjunction with specific embodiment, further set forth the present invention., these embodiment are not used in restriction scope of the present invention but only limiting to the present invention is described.
Embodiment 1
According to TiNb 2O 7In the proportioning of each element get highly purified TiO respectively 2Powder and Nb 2O 5Powder and right amount alcohol are put into mixing tank, and ball milling is 10 hours then, and dry under 50～70 ℃, the heating rate with 5 ℃/min is warming up between 1200～1400 ℃ in air atmosphere again, and is incubated 24 hours, is cooled to room temperature subsequently, obtains pure phase TiNb 2O 7Sample.Fig. 1 has provided pure phase TiNb 2O 7The X ray diffracting spectrum of sample.Experiment shows: Ti and Nb element are at TiNb 2O 7In mutual occupy-place meeting the sealing strength ratio of its XRD is exerted an influence, and this mutual occupy-place is easy to take place in the process of preparation material.
Embodiment 2
Pure phase TiNb to embodiment 1 preparation 2O 7Material is done the UV, visible light optical absorption spectra, and the result is as shown in Figure 2, can be known TiNb by Fig. 2 2O 7The ABSORPTION EDGE of material is greatly about 420nm; Can obtain its band gap at 2.95eV through conversion; Can know that in conjunction with first principle calculating it is the material of indirect band gap; Indicate that its short wavelength's section in visible absorption has potential application, can be used as a kind of material of light absorption, perhaps in photovoltaic cell, use.Test simultaneously and calculate and show that it has potential application in electrochromism.
Pure phase TiNb with embodiment 1 preparation 2O 7Material and ionic liquid [EMIm] [N (CN) 2] evenly mix after; At tube furnace, in the argon gas atmosphere, the mixture that obtains is warming up between 500～700 ℃ from room temperature, and under this temperature, kept 4 hours with 5 ℃/minute speed, ionic liquid is fully reacted, obtain composite material C after the cooling 0.91N 0.09-TiNb 2O 7, this composite material is done the UV, visible light optical absorption spectra, the result sees Fig. 2, can be known by this figure, composite material C of the present invention 0.91N 0.09-TiNb 2O 7Absorption to light has certain change, the ABSORPTION EDGE that this material that contains boron carbon or carbon nitrogen or boron carboritride can effectively be regulated the titanium niobate material.
Embodiment 3
Pure phase TiNb with embodiment 1 preparation 2O 7Sample is done the experiment of thermogravimetric differential thermal in Ar atmosphere, the result is shown in Fig. 3 (a).There is tangible suction to put the oxygen phenomenon 100 ℃ to 600 ℃ scopes, indicating TiNb 2O 7It possibly be a kind of potential hydrogen-storing material.
Composite material C with embodiment 2 preparations 0.91N 0.09-TiNb 2O 7At Ar and O 2Do the experiment of thermogravimetric differential thermal in the mixed atmosphere, tangible weightlessness is arranged, the oxidation that this ascribes boron carbon or carbon nitrogen or boron carboritride to breaks away from due to the surface then, shown in Fig. 3 (b).
Embodiment 4
According to TiNb 2O 7In the proportioning of each element get highly purified TiO respectively 2Powder and Nb 2O 5Powder and right amount alcohol are put into mixing tank, and ball milling is 10 hours then, and be dry down at 50～70 ℃; Heating rate with 5 ℃/min is warming up between 1200～1400 ℃ in air atmosphere again; And be incubated 24 hours, and be cooled to room temperature subsequently, obtain pure phase titanium niobate TiNb 2O 7Material.
TiNb with preparation 2O 7With acetylene black and PVDF, be that 80%, 15% and 5% proportioning is prepared into electrode according to the quality percentage composition, as an electrode of half-cell,, use 1mol/L LiPF to the electrodes use lithium metal 6/ vinyl carbonate (EC)-divinyl carbonic ester (DEC) (volume ratio of EC and DEC 1: 1) is assembled into battery and this battery is carried out charge-discharge test as electrolyte in glove box.Voltage range is 3.0V～1.0V.Analog result is seen table 1.
Embodiment 5
According to TiNb 2O 7In the proportioning of each element get highly purified TiO respectively 2Powder and Nb 2O 5Powder and right amount alcohol are put into mixing tank, and ball milling is 10 hours then, and be dry down at 50～70 ℃; Heating rate with 5 ℃/min is warming up between 1200～1400 ℃ in air atmosphere again; And be incubated 24 hours, and be cooled to room temperature subsequently, obtain pure phase titanium niobate TiNb 2O 7Material.
Then, with the TiNb for preparing 2O 7Material is heating several hours in 700～900 ℃ the temperature range under argon, nitrogen atmosphere, can obtain containing the titanium niobate material TiNb in aerobic room 2O 6.9Copy embodiment 4 to do charge-discharge test.Analog result is seen table 1.
Embodiment 6
Copy embodiment 5 preparations to contain the titanium niobate material TiNb in aerobic room 2O 6.8Sample is done charge-discharge test.Analog result is seen table 1.
Embodiment 7
According to TiNb 2O 7In the proportioning of each element get highly purified TiO respectively 2Powder and Nb 2O 5Powder and right amount alcohol are put into mixing tank, and ball milling is 10 hours then, and be dry down at 50～70 ℃; Heating rate with 5 ℃/min is warming up between 1200～1400 ℃ in air atmosphere again; And be incubated 24 hours, and be cooled to room temperature subsequently, obtain pure phase titanium niobate TiNb 2O 7Material.
Then, with the TiNb for preparing 2O 7Material is heating several hours in 700～900 ℃ the temperature range under argon, nitrogen atmosphere, can obtain containing the titanium niobate material TiNb in aerobic room 2O 6.9
With the titanium niobate material TiNb that contains the aerobic room that obtains 2O 6.9With [EMIm] [N (CN) 2] evenly mix after; At tube furnace, in the argon gas atmosphere, the mixture that obtains is warming up between 500～700 ℃ from room temperature, and under this temperature, kept 4 hours with 5 ℃/minute speed, ionic liquid is fully reacted, obtain composite material: C after the cooling 0.9N 0.1-TiNb 2O 6.9Copy embodiment 4 to do charge-discharge test.Analog result is seen table 1.
Embodiment 8
Copy embodiment 7 that the titanium niobate material sample that contains the aerobic room of pure sample is evenly mixed back preparation B with triphenyl borine 0.08C 0.92-TiNb 2O 6.9Composite material is done charge-discharge test.Analog result is seen table 1.
Embodiment 9
Copy embodiment 7 that the titanium niobate material sample that contains the aerobic room of pure sample evenly is mixed with B with [BCNIm] [Tf2N] 0.07C 0.80N 0.13-TiNb 2O 6.9Composite material is done charge-discharge test.Analog result is seen table 1.
Embodiment 10
According to TiNb 2O 7In the proportioning of each element get the highly purified TiO of 798.7mg respectively 2Powder, the highly purified Nb of 2658.1mg 2O 5Powder and about 15 milliliters alcohol are put into mixing tank; Ball milling is 10 hours then, and dry under 50～70 ℃, the heating rate with 5 ℃/min is warming up between 1200～1400 ℃ in air atmosphere again; And be incubated 24 hours; Be cooled to room temperature subsequently, with handling 4 hours the TiN that promptly obtains in 500 ℃ of ammonias of the product that obtains 0.01Nb 2O 7, copy embodiment 4 to do charge-discharge test, analog result is seen table 1.
Embodiment 11
According to TiNb 2O 7In the proportioning of each element get the highly purified TiO of 751.3mg respectively 2The highly purified Nb of powder and 2658.1mg 2O 5Powder and about 15 milliliters alcohol are put into mixing tank, and ball milling is 10 hours then, and dry under 50～70 ℃, the heating rate with 5 ℃/min is warming up between 1200～1400 ℃ in air atmosphere again, and is incubated 24 hours, is cooled to room temperature subsequently, obtains Ti 0.99Nb 2O 7Sample.Copy embodiment 4 in 3.0V～1.0V voltage range, to carry out charge-discharge test then.Analog result is seen table 1.
Embodiment 12
Copy embodiment 11 preparation Ti 0.96Nb 2O 7Material is done charge-discharge test.Analog result is seen table 1.
Embodiment 13
According to TiNb 2O 7In the proportioning of each element get the highly purified TiO of 758.9mg respectively 2Powder, the highly purified Al of 51.0mg 2O 3The highly purified Nb of powder and 2658.1mg 2O 5Powder and about 15 milliliters alcohol are put into mixing tank, and ball milling is 10 hours then, and dry under 50～70 ℃, the heating rate with 5 ℃/min is warming up between 1200～1400 ℃ in air atmosphere again, and is incubated 24 hours, is cooled to room temperature subsequently, obtains Ti 0.9Al 0.05Nb 2O 7Sample.Copy embodiment 4 in 3.0V～1.0V voltage range, to carry out charge-discharge test then.Analog result is seen table 1
Embodiment 14
Copy embodiment 11 with Ti 0.9Al 0.05Nb 2O 7Sample evenly is mixed with B with [BCNIm] [Tf2N] 0.03C 0.87N 0.1-Ti 0.9Al 0.05Nb 2O 7Composite material is done charge-discharge test.Analog result is seen table 1.
Embodiment 15
Pure phase titanium niobate TiNb with embodiment 1 preparation 2O 7Material and [EMIm] [N (CN) 2] evenly mix after; At tube furnace, in the argon gas, the mixture that obtains is warming up between 500～700 ℃ from room temperature, and under this temperature, kept 4 hours with 5 ℃/minute speed, ionic liquid is fully reacted, obtain composite material: C after the cooling 0.91N 0.09-TiNb 2O 7
C with preparation 0.91N 0.09-TiNb 2O 7With acetylene black and PVDF be that 80%, 15% and 5% proportioning is prepared into electrode according to the quality percentage composition, as an electrode of half-cell,, use 1mol/L LiPF to the electrodes use lithium metal 6/ vinyl carbonate (EC)-divinyl carbonic ester (DEC) (volume ratio of EC and DEC 1: 1) is assembled into battery it is carried out charge-discharge test as electrolyte in glove box.Voltage range is 3.0V～1.0V.Fig. 4 has provided the composite material C for preparing in the present embodiment 0.91N 0.09-TiNb 2O 7Charging and discharging curve, Fig. 5 has provided the cyclic process of this composite material.As can beappreciated from fig. 4 it has higher first all efficiency for charge-discharges, but because particle is bigger, approximately 20um cause this composite material that contains boron carbon or carbon nitrogen or boron carboritride not react completely, thereby capacity is lower than expection.Fig. 5 can find out that its capacity still has performance preferably after 20 weeks, good cyclicity, and stabilization efficiency is more than 99%.Analog result is seen table 1.
Embodiment 16
With the pure phase titanium niobate TiNb of embodiment 1 preparation 2O 7Material sample is with after triphenyl borine evenly mixes; At tube furnace, in the argon gas, the mixture that obtains is warming up between 500～700 ℃ from room temperature, and under this temperature, kept 4 hours with 5 ℃/minute speed, ionic liquid is fully reacted, obtain composite material: B after the cooling 0.08C 0.92-TiNb 2O 7
With the composite material B that makes 0.08C 0.92-TiNb 2O 7With acetylene black and PVDF be that 80%, 15% and 5% proportioning is prepared into electrode according to the quality percentage composition, as an electrode of half-cell,, use 1mol/L LiPF to the electrodes use lithium metal 6/ vinyl carbonate (EC)-divinyl carbonic ester (DEC) (volume ratio of EC and DEC 1: 1) is assembled into battery it is carried out charge-discharge test as electrolyte in glove box.Analog result is seen table 1.
Embodiment 17
With the pure phase titanium niobate TiNb of embodiment 1 preparation 2O 7Material sample is with after [BCNIm] [Tf2N] evenly mixes; At tube furnace, in the ammonia, the mixture that obtains is warming up between 500～700 ℃ from room temperature, and under this temperature, kept 4 hours with 5 ℃/minute speed, ionic liquid is fully reacted, obtain composite material: B after the cooling 0.05C 0.84N 0.11-TiNb 2O 7
With the composite material B that makes 0.05C 0.84N 0.11-TiNb 2O 7With acetylene black and PVDF be that 80%, 15% and 5% proportioning is prepared into electrode according to the quality percentage composition, as an electrode of half-cell,, use 1mol/L LiPF to the electrodes use lithium metal 6/ vinyl carbonate (EC)-divinyl carbonic ester (DEC) (volume ratio of EC and DEC 1: 1) is assembled into battery it is carried out charge-discharge test as electrolyte in glove box.Voltage range is 3.0V～1.0V.Analog result is seen table 1.
Embodiment 18
With the pure phase titanium niobate TiNb of embodiment 1 preparation 2O 7Material sample is with after sucrose evenly mixes; At tube furnace, in the argon gas, the mixture that obtains is warming up between 600 ℃ from room temperature, and under this temperature, kept 4 hours with 5 ℃/minute speed, obtain composite material: C-TiNb after the cooling 2O 7(the titanium niobate material that carbon coats).
With the composite material C-TiNb that makes 2O 7With acetylene black and PVDF be that 80%, 15% and 5% proportioning is prepared into electrode according to the quality percentage composition, as an electrode of half-cell,, use 1mol/L LiPF to the electrodes use lithium metal 6/ vinyl carbonate (EC)-divinyl carbonic ester (DEC) (volume ratio of EC and DEC 1: 1) is assembled into battery it is carried out charge-discharge test as electrolyte in glove box.Voltage range is 3.0V～1.0V.Analog result is seen table 1.
Embodiment 19
The TiNb for preparing pure phase according to the method among the embodiment 4 2O 7Sample obtains the nano-TiNb of about 150nm then after 24 hours at ball milling on the high energy ball mill 2O 7Particle is done charge-discharge test according to embodiment 4.Analog result is seen table 1.
Embodiment 20
According to the method among the embodiment 7 with sample and [EMIm] [N (CN) 2] evenly prepare C after the mixing 0.93N 0.07-nano-TiNb 2O 7Sample is done charge-discharge test according to embodiment 4.Analog result is seen table 1.
Embodiment 21
The TiNb for preparing pure phase according to the method among the embodiment 4 2O 7Sample obtains the nano-TiNb of about 150nm then after 24 hours at ball milling on the high energy ball mill 2O 7Particle, and then handled 8 hours under reducing atmosphere argon gas and the hydrogen environment, the nano-TiNb in aerobic room got 2O 6.92, then with sample and [EMIm] [N (CN) 2] evenly prepare C under the inert atmosphere of mixing back 0.92N 0.08-nano-TiNb 2O 6.92Sample is done charge-discharge test according to embodiment 4.Analog result is seen table 1.
Embodiment 22
According to the method among the embodiment 7 sample and triphenyl borine are evenly mixed back preparation B 0.06C 0.94-nano-TiNb 2O 7Sample is done charge-discharge test according to embodiment 4.Analog result is seen table 1.
Embodiment 23
According to the method among the embodiment 7 sample is evenly mixed back preparation B with [BCNIm] [Tf2N] 0.07C 0.83N 0.1-nano-TiNb 2O 7Sample is done charge-discharge test according to embodiment 4.Analog result is seen table 1.
Embodiment 24
According to Li 0.1TiNb 2O 7In the proportioning of each element get highly purified TiO respectively 2Powder, Nb 2O 5Powder and excessive Li 2CO 3And right amount alcohol puts into mixing tank, and ball milling is 10 hours then, and is dry down at 50～70 ℃; Heating rate with 5 ℃/min is warming up between 800～1000 ℃ in air atmosphere again; And be incubated 24 hours, and be cooled to room temperature subsequently, obtain the titanium niobate Li of the preparatory embedding lithium of pure sample 0.1TiNb 2O 7Material.
Li with preparation 0.1TiNb 2O 7Material and acetylene black and PVDF are that 80%, 15% and 5% proportioning is prepared into electrode according to mass percent, as an electrode of half-cell, to the electrodes use lithium metal.Use 1mol/L LiPF 6/ vinyl carbonate (EC)-divinyl carbonic ester (DEC) (volume ratio of EC and DEC 1: 1) is assembled into battery and its battery is carried out charge-discharge test as electrolyte in glove box.Voltage range is 3.0V～1.0V.Analog result is seen table 1.
Table 1 is by the charge-discharge test result of the battery of the titanium niobate negative material preparation of embodiment 4-24
Figure BSA00000361669600131

Claims (10)

1. titanium niobate composite material, this composite material has following general formula:
B xC yN z-L aTi bM cNb dO e
Wherein, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound;
L is Li or Na, is preferably Li;
M is selected from a kind of among Al, B, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta, N and the P;
X, y, z, a, b, c, d and e represent molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0≤a≤0.2,0.8＜b≤1.1,0≤c＜0.2,1.95＜d≤2.1,6.8≤e≤7, and x and z are not zero simultaneously;
Preferably, 0≤x＜1,0＜y＜1,0＜z＜1; More preferably, x=0,0＜y＜1,0＜z＜1.
2. composite material according to claim 1 is characterized in that, said boron carbon or carbon nitrogen or the boron carbon nitrogen compound B of containing xC yN zBe coated on L aTi bM cNb dO eThe surface of material.
3. composite material according to claim 1 and 2 is characterized in that, in the said composite material, and said boron carbon or carbon nitrogen or the boron carbon nitrogen compound B of containing xC yN zThe quality percentage composition be 0.1%-20%, be preferably 1%-10%.
4. according to each described composite material in the claim 1 to 3, it is characterized in that, when x=0, said B xC yN zIn the quality percentage composition of nitrogen be 0.01%-30%, be preferably 0.1%-15%, the quality percentage composition of nitrogen in said composite material is 0.001%-6%, is preferably 0.1%-1.5%; When x ≠ 0, said B xC yN zThe quality percentage composition of middle nitrogen is 0%-20%, is preferably 0.1%-10%, and the quality percentage composition of nitrogen in said composite material is 0%-4%, is preferably 0.1%-1%.
5. according to each described composite material in the claim 1 to 4, it is characterized in that, when z=0, said B xC yN zThe quality percentage composition of middle boron is 0.01%-15%, is preferably 0.1%-8%, and the quality percentage composition of boron in said composite material is 0.001%-3%, is preferably 0.1%-1.5%; When z ≠ 0, said B xC yN zThe quality percentage composition of middle boron is 0%-10%, is preferably 0.1%-5%, and the quality percentage composition of boron in said composite material is 0%-2%, is preferably 0.1%-1%.
6. the preparation method of each described composite material in the claim 1 to 5, this preparation method comprises:
With L aTi bM cNb dO eEvenly mix with the material that contains boron carbon or carbon nitrogen or boron carboritride; At inert atmosphere, for example in nitrogen or the argon gas, said mixture is warming up to 400～700 ℃ from room temperature with 5 ℃/minute speed; And under this temperature, kept 4 hours; Fully after the reaction, cooling obtains said composite material;
Wherein, L is Li or Na, is preferably Li;
M is selected from a kind of among Al, B, V, Cr, Mn, Fe, Co, Ni, Ce, Y, Zr, Mo, La, Ta, N and the P;
X, y, z, a, b, c, d and e represent molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0≤a≤0.2,0.8＜b≤1.1,0≤c＜0.2,1.95＜d≤2.1,6.8≤e≤7, and x and z are not zero simultaneously;
Preferably; The said material that contains boron carbon or carbon nitrogen or boron carboritride is the two fluoroform sulfimide salt, 1 of 1-ethyl-3-methylimidazole dicyanamide salt, 1-butyl-3-methylimidazole; 4,5-trimethyl-3-perfluoro capryl-1,2; 4-triazole tetrafluoroborate, 1-cyanogen methyl-3-methyl imidazolium tetrafluoroborate, 1, two (cyanogen) tetrafluoroborates of 3-, triphenyl borine, Glucosamine or phthalocyanine.
7. preparation method according to claim 6 is characterized in that, said L aTi bM cNb dO eThe preparation method comprise the steps:
According to L aTi bM cNb dO eIn the proportioning of each element, with TiO 2Powder, Nb 2O 5After powder, L source and the M source batching, add solvent, for example absolute ethyl alcohol, water or acetone diluted become white paste; With said pastel ball milling after 10-24 hour; Dry under 50-70 ℃, the cooling back is warming up between 1200～1400 ℃ with 5 ℃/minute speed, and after being incubated 24 hours; Cooling promptly gets;
Preferably, said L source is the lithium source, for example is lithium carbonate, lithium acetate, lithium hydroxide or lithium oxalate;
Preferably, said M source is the oxide that contains Al, B, La or Ta, or contains the material of Al, B, La or Ta oxide after the decomposes;
Preferably, said L aTi bM cNb dO eThe preparation method also comprise the product that obtains carried out 24 hours high energy millings, obtain 100-500nm, be preferably the step of 200nm granular materials;
Preferably, said L aTi bM cNb dO eThe preparation method also comprise with the product that obtains under temperature 700-900 ℃ reducing atmosphere, for example hydrogen; Perhaps inert atmosphere, for example step of heat treatment in nitrogen or the argon gas.
8. preparation method according to claim 6 is characterized in that, said L aTi bM cNb dO eThe preparation method comprise the steps:
(1) titanium tetraisopropylate and ammoniacal liquor reaction are formed white precipitate, add nitric acid then white precipitate is dissolved fully, form transparent TiO (NO 3) 2Solution;
(2) with Nb (OH) 5With citric acid be that 1: 5 ratio is dissolved in the deionized water with mol ratio, then, add the TiO (NO of preparation in the step (1) 3) 2Solution, the mixed liquor that obtains are incubated down at 40～60 ℃ and form colloidal sol, continue heating and also remain between 80～100 ℃, form gel;
(3) gel that step (2) is made is warming up between 1000～1300 ℃ with 5 ℃/minute heating rate, and is incubated 24 hours, and cooling promptly gets;
Preferably, said L aTi bM cNb dO eThe preparation method also comprise the product that obtains carried out 24 hours high energy millings, obtain 100-500nm, be preferably the step of the granular materials of 200nm;
Preferably, said L aTi bM cNb dO eThe preparation method also comprise with the product that obtains under temperature 700-900 ℃ reducing atmosphere, for example hydrogen; Perhaps inert atmosphere, for example step of heat treatment in nitrogen or the argon gas.
9. negative pole, this negative pole comprise collector and load on the negative material on this collector, it is characterized in that said negative material contains each described composite material in the claim 1 to 5.
10. lithium battery, this battery comprises positive pole, negative pole and electrolyte, it is characterized in that, said negative pole is the described negative pole of claim 9.
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